CN102796230A - Method for preparing silicone acrylic emulsion with high solid content and high silicon content - Google Patents
Method for preparing silicone acrylic emulsion with high solid content and high silicon content Download PDFInfo
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Abstract
The invention relates to a method for preparing a silicone acrylic emulsion with high solid content (of over 50 percent), high organic silicon content (of over 15 percent) and low emulsifier consumption (of less than 2.5 percent), in particular a silicone acrylic emulsion for preparing high-grade exterior wall coating materials. The method comprises steps of preparing a vinyl polysiloxane emulsion by using octamethylcyclotetrasiloxane, tetravinyl tetramethylcyelo tetrasiloxane, dodecylbenzene sulfonic acid, sodium dodecyl benzene sulfonate, a non-ionic emulsifier NP-40 and deionized water through acid catalyzed ring opening, and performing silicone acrylic emulsion copolymerization of the vinyl polysiloxane emulsion and acrylic monomers in the presence of a thermal initiator to prepare the stable silicone acrylic emulsion with high solid content, high organic silicon content and low emulsifier consumption. By the method, problems that the silicon content cannot be improved substantially, the solid content is low and the emulsifier consumption is high in the preparation of the silicone acrylic emulsion are effectively solved. The silicone acrylic emulsion has excellent weather resistance, stain resistance, water resistance and the like, and has high cost performance; and the application range of the silicone acrylic emulsion is greatly widened.
Description
Technical field
The present invention relates to a kind of preparation method of organosilicon crylic acid latex; The preparation method of particularly a kind of high solids content (greater than 50%), high organosilicon content (greater than 15%) and low emulsifying agent consumption (less than 2.5%) organosilicon crylic acid latex is particularly useful for the organosilicon crylic acid latex that high-grade exterior coating is prepared.
Background technology
Polyacrylate emulsion is widely used in the production of emulsion for architecture coating with advantages such as its good film-forming property, intensity height and cohesiveness are strong, but has shortcomings such as weather resisteant, water tolerance and contamination resistance simultaneously, has limited its further application.Along with people's is to greenization, high performance and the multifunction requirement of coating products, and the propenoate latex coating meets the demands very slowly, especially as building external paint, must have good weathering resistance, water tolerance and contamination resistance.Fluorine modification in recent years and organosilicon-modified acrylate emulsion become the representative of high-weatherability latex coating; Organosilicon-modified acrylate emulsion particularly; Owing to organosilicon has the surface property that characteristics such as Si-O key bond energy is big, surface energy is low, molecular flexibility is big have many uniquenesses, with the two New Emulsion material that combines and to obtain both excellent properties.And compare with fluorine carbon emulsion; The weathering resistance of silicon third latex coating can compare favourably with fluorine carbon emulsion paint; Contamination resistance then is superior to fluorine carbon emulsion paint, and production cost is also low than fluorine carbon emulsion, and the processing unit of production is close with acrylic ester emulsion; Being easy to realize transformation and the large-scale production to acrylic ester emulsion, is the main developing direction of high-performance weather-proof property water-borne coatings.
At present; The organosilicon component concentration is general all less than 10% of polymer quality in the organosilicon crylic acid latex that is provided on the domestic and international market; Even in organosilicon crylic acid latex in the rubber-emulsion paint is 50%, organosilyl actual content can not represent its due various over-all propertieies well also below 3% in filming.In addition, existing organosilicon crylic acid latex ubiquity emulsifying agent consumption is higher, the low shortcomings such as (＜50%) of system solid content, and this high emulsifying agent consumption, the shortcoming of low-grade polymer content has also limited its widespread use in industrial production.Therefore, reduce the emulsifying agent consumption, improve polymer content; And the substantive content of organosilicon in the raising polymkeric substance; Prepare and have high organosilicon content of high solids content and low emulsifying agent consumption simultaneously, the organosilicon crylic acid latex of excellent combination property is the key of preparation high-grade paint.
Based on the problem of above existence, the investigator has also carried out number of research projects both at home and abroad, and related patent U.S. Patent No. and document also have report.Patent CN1546542A discloses a kind of novel process of organosilicon crylic acid latex of synthetic high organosilicon content (15%～25%); Prepared emulsion film has very strong hydrophobicity; But its method adopts the ring-opening polymerization of cyclosiloxane and the radical polymerization of vinyl monomer to carry out synchronously, and both require difference to the reaction medium pH value, and the former need carry out in acidity or alkaline medium; The latter then need carry out under little neutrallty condition; Will certainly cause in the organosilicon crylic acid latex product organosilicon content can't obtain substantive the raising like this, solid content is only about 40% simultaneously, and the emulsifying agent consumption is 4% of a monomer consumption; Also added a certain amount of assistant for emulsifying agent, these can influence the raising of the over-all properties of emulsion to a great extent.Patent CN1796428A discloses with the organoalkoxysilane coupling agent as an organosilane monomer; Adopt mini-emulsion polymerization to synthesize a kind of high-performance high silane content modified polyacrylate emulsion; But organosilicon content is 10% of monomer total amount; And solid content is 47%, has also added a certain amount of assistant for emulsifying agent.It is monomer that CN1629202A discloses with vinyltriethoxysilane, vinylformic acid and propenoate; Under the provide protection of protective colloid and hydrolysis inhibitor, synthesized a kind of organosilicon content greater than 15% nucleocapsid structure organosilicon crylic acid latex, but solid content also is lower than 50%; And the emulsifying agent consumption reaches 8%; The consumption of protective colloid and hydrolysis inhibitor is also higher, with having a strong impact on the water resistance of filming, also is unfavorable for environmental protection.Patent CN101781390A discloses a kind of preparation method of used for building exterior wall nucleocapsid structure high silicon content organosilicon crylic acid latex; It prepares unsaturated organosilicon oxygen alkane oligopolymer emulsion through cyclosiloxane and comes modified polyacrylate, and the highest add-on of its organosilicon can account for 20% of siloxane-acrylate copolymer.But only between 36%～45%, the emulsifying agent consumption is also higher for its product solid content.Patent CN101798369A also discloses a kind of preparation method of high silicon content organosilicon crylic acid latex; Organosilicon content accounts for more than 10% of emulsion system in the gained emulsion; It is with the organoalkoxysilane coupling agent as an organosilane monomer, through adding hydrolysis inhibitor and adopt redox initiator to implement, but solid content is also below 50%; Simultaneously also introduce some auxiliary agents, be unfavorable for the raising of over-all properties.Kingdom builds etc. in " development of high silicon content organic silicon-acrylate emulsion " delivered in the 43rd 2 phases of volume of " Shanghai coating " January in 2005 and adopts hydrolysis inhibition method; So that the vinylsiloxane monomer and the acrylate monomer of facile hydrolysis do not carry out letex polymerization; Make organosilicon content and reach 20% organic silicon-acrylate emulsion, but emulsifying agent large usage quantity and solid content are lower.Employing has a branched structure in " the synthetic and performance of branching type organosilicon acrylic ester copolymerization emulsion " that Tang Minfeng etc. delivered in the 24th the 1st phase of volume of " fine chemistry industry " January in 2007 reactive an organosilane monomer and MPS silane coupling agent and acrylic ester monomer carry out emulsion copolymerization; Synthesize the highest organosilicon content and reached 10% stable high silicon content organosilicon crylic acid latex; But also have same problem, solid content is lower than 50%.In addition, also have other some investigators also to do similar research work, " research of room temperature preparation high silicon content VTES/St/MMA copolymer emulsion " delivered in the 30th the 1st phase of volume of " modern chemical industry " January in 2010 such as Yin Changjie etc.; " the synthetic and stability of the low temperature of silicon-third nuclear/shell emulsion " that Ge Chengyue etc. delivered in the 25th the 4th phase of volume of " polymer material science and engineering " April in 2009; " development of high silicon content organic silicon-acrylate emulsion " that Hu Zhongyu delivered in the 36th the 1st phase of volume of " New Chemical Materials " January in 2008 etc.; All synthesized the organosilicon crylic acid latex of organosilicon content between 10%-15%; But all have identical problem: solid content is lower, and the partial emulsifier consumption is higher.
Existing technology shows, when organosilicon content is low, the performance of organosilicon crylic acid latex improved limited, do not reach the effect of modification; The emulsifying agent consumption very little, when increasing organosilicon content or solid content XOR simultaneously during the two content, the bad stability of emulsion is prone to cohesion; If but increase organosilicon content and reduce solid content, then can increase and produce and cost such as transportation, and the further widespread use of restriction organosilicon crylic acid latex; The emulsifying agent consumption is many, has influenced the hydrophobicity effect of an organosilane monomer again to a certain extent, causes the emulsion film water tolerance to reduce.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the deficiency and the defective of prior art; Provide a kind of and when low emulsifying agent consumption (less than 2.5%), have higher solids content (greater than 50%) simultaneously, higher organosilicon content (greater than 15%); Stable good high performance silicon emulsion; This organosilicon crylic acid latex has excellent characteristics such as weathering resistance, water tolerance and contamination resistance ability, and good with the compatibility of color stuffing, is particularly useful for disposing the base-material of high-grade exterior coating.
Another object of the present invention also provides the preparation method of above-mentioned organosilicon crylic acid latex.
The preparation method of the low emulsifying agent consumption organosilicon crylic acid latex of the high organosilicon content of a kind of high solids content mainly realizes through following technical scheme, comprises step:
(1) contain the preparation of vinyl polysiloxane emulsion:
Get octamethylcyclotetrasiloxane 30%～40%, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 10%～20%, Witco 1298 Soft Acid 1%～10%, X 2073 1%～5%, emulsifying agent NP-401%～5%, deionized water 40%～60% by quality;
Witco 1298 Soft Acid, X 2073, emulsifying agent NP-40 and deionized water joined in the reaction kettle stir; Warming-in-water to 60～85 ℃ add an organosilane monomer mixture in 2h-3h, insulation continues reaction 3h; Stop heating; Naturally cool to room temperature, be neutralized to neutrality, obtain containing the vinyl polysiloxane emulsion with 10% aqueous sodium carbonate
(2) preparation of silicon third copolymer emulsion:
Take off the row component by quality: step 1) preparation contain vinyl polysiloxane emulsion 40-60%, acrylic ester monomer 40-50%, initiator 0.1-0.5%, pH value regulator 0.01-0.1%, molecular weight regulator 1%, deionized water 30-40%;
To contain vinyl polysiloxane emulsion, acrylic ester monomer mixture total amount 15%, 20% being added in the reaction kettle of initiator and pH value regulator total amount; Be warming up to 75-85 ℃; The about 30min of isothermal reaction blue light this moment is sufficient and do not have the backflow monomer and produce; Constant temperature drips the mixture of remaining organosilicon and acrylic ester monomer and the mixture of remaining initiator and pH value regulator then, and the dropping time is about 2.5-3.5h; Dropwise isothermal reaction 0.5h, be warming up to 85-95 ℃ then, continue reaction 1-1.5h, stop heating, obtain described organosilicon crylic acid latex.
Said an organosilane monomer mixture by octamethylcyclotetrasiloxane and tetramethyl-tetrem alkene cyclotetrasiloxane with 9: 1-5: 1 mass ratio is formed; Concrete consumption or proportioning are according to the purposes decision of product; The former consumption increase can improve flexibility, the winter hardiness of product, and the increase of latter's consumption can improve rigidity, the thermotolerance of product;
Said acrylic ester monomer is meant two or more the mixture that is selected from vinylformic acid, methylacrylic acid, TEB 3K, methyl acrylate, ethyl propenoate, propyl acrylate, Bing Xisuandingzhi or the Isooctyl acrylate monomer; Concrete consumption or proportioning are according to the purposes decision of product; Vinylformic acid and the increase of methylacrylic acid consumption can improve the stability of product; Reduce the consumption of emulsifying agent, but can reduce the water tolerance of product; TEB 3K increases the rigidity of product glued membrane, and all the other monomer increases can improve the flexibility of product glued membrane successively;
Said compound emulsifying agent is at least two kinds of negatively charged ion-nonionic emulsifying agents that material is formed in X 2073, sodium lauryl sulphate or the octyl group polyethenoxy ether class, and the proportioning of negatively charged ion and nonionic is 4: 1～2: 1;
Said catalyzer is a Witco 1298 Soft Acid; Acrylic or methacrylic acid; They are both as the acid catalyst of ring-opening polymerization; The emulsifying effect, the especially latter that also have tensio-active agent simultaneously concurrently be because as can participating in main chain polymeric surface active monomer, can guarantee under the stable prerequisite of polymer emulsion product, significantly to reduce the total consumption of emulsifying agent;
Said initiator is a persulphate, mainly is ammonium persulphate or Potassium Persulphate, and its consumption can be decided according to polymerization temperature, and consumption improves with selected polymerization temperature usually and reduces.
Described molecular weight regulator is a lauryl mercaptan;
Said PH buffer reagent is sodium hydrogencarbonate, Sodium phosphate, dibasic or SODIUM PHOSPHATE, MONOBASIC;
Compared with prior art, the present invention has following characteristics:
1, owing to employed an organosilane monomer raw material sources among the present invention are extensive, price is cheaper, under identical performance, can effectively reduce the emulsion production cost.
What 2, prepare among the present invention contains the vinyl polysiloxane emulsion, and monomer conversion is high, and size distribution is even; Good emulsion stability; Its chemical structure is the line style unsaturated polyester siloxanes with certain chain length, and side chain is vinyl, methyl, and it is sterically hindered effectively to reduce the organosilicon ring body structurc; More help carrying out copolymerization with acrylic ester monomer; Increase the introducing amount and the chain length thereof of Si-O-Si key in the acrylic ester polymer simultaneously, give full play to its premium properties, its highest add-on accounts for 20% of siloxane-acrylate copolymer; Simultaneously, the ZGK 5 that is generated has fine emulsifying effectiveness, can effectively reduce the consumption of emulsifying agent in the organosilicon crylic acid latex, reduces the generation of condensation prod, strengthens the stability of emulsion, and also can increase the consistency between two phases.
3, adopt open loop letex polymerization and radical polymerization proceed step by step, satisfied the requirement of polyreaction, make that organosilicon content can access substantive the raising in the organosilicon crylic acid latex reaction medium.
4, since in the organosilicon crylic acid latex of the present invention solid content and organosilicon content all higher, so not only can reduce the cost of production and transport greatly, enlarge its range of application, and have good contamination resistance and weathering resistance with its prepared coating.Amounting under the condition of identical solid content, saving of labor of the present invention, material-saving, the advantage that saves time, economizes the energy are very remarkable.
5, product organosilicon crylic acid latex of the present invention has that solid content height, organosilicon content are high, the low and shelf-stable of emulsifying agent consumption, not only has performances such as good weathering resistance, contamination resistance, contamination resistance, and dry rapidly, advantages such as the transparency and good fluidity.
Embodiment
For the present invention is described better, in conjunction with embodiment technology of the present invention is given to explain further, but the present invention is not limited in following embodiment.
Embodiment 1:
1) contains the preparation of vinyl polysiloxane emulsion: earlier 4g Witco 1298 Soft Acid, 2g X 2073,2g NP-40,60g deionized water are joined in the reaction kettle; Stir fully dissolving; Be warming up to 80 ℃ afterwards; Then 30g octamethylcyclotetrasiloxane, 10g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane mixing an organosilane monomer slowly are added dropwise in 3h in the reaction kettle, insulation reaction 3h naturally cools to room temperature; Be neutralized to neutrality with 10% aqueous sodium carbonate at last, must contain the vinyl polysiloxane emulsion.
The gained emulsion solid content is greater than 35%, molecular weight 2000-5000, and package stability was greater than 3 months.
2) preparation of silicon third copolymer emulsion:
35g is contained vinyl polysiloxane emulsion, 42.5g Bing Xisuandingzhi, 42.5g TEB 3K, 3g vinylformic acid and 20g deionized water joins in the single port flask, under high-speed stirring in advance emulsification 0.5h to get pre-emulsion for use; It is for use that while adding 0.4g ammonium persulphate, 0.1g sodium hydrogencarbonate and 15g deionized water in another flask obtains initiator solution.
In disposing the four-hole round-bottomed flask of TM, whisking appliance, reflux condensing tube and constant pressure funnel, 15g deionized water and 25g are contained the vinyl polysiloxane emulsion add and wherein stir, be warming up to 80 ℃ behind the logical nitrogen 0.5h; Drop into 10% pre-emulsion and 15% initiator solution simultaneously; Reaction 0.5h begins to drip remaining pre-emulsion and initiator solution simultaneously, dropwises in the 3h, is warming up to 85 ℃ behind the insulation 0.5h and continues reaction 1h; Stop heating; Naturally cool to room temperature, filter discharging, promptly obtain described silicon third copolymer emulsion.
Embodiment 2:
1) contains the preparation of vinyl polysiloxane emulsion: earlier 4g Witco 1298 Soft Acid, 2g X 2073,2g NP-40,60g deionized water are joined in the reaction kettle; Stir fully dissolving; Be warming up to 80 ℃ afterwards; Then 25g octamethylcyclotetrasiloxane, 15g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane mixing an organosilane monomer slowly are added dropwise in 3h in the reaction kettle, insulation reaction 3h naturally cools to room temperature; Be neutralized to neutrality with 10% aqueous sodium carbonate at last, must contain the vinyl polysiloxane emulsion.
The gained emulsion solid content is greater than 35%, molecular weight 2000-5000, and package stability was greater than 3 months.
2) preparation of silicon third copolymer emulsion:
30g is contained vinyl polysiloxane emulsion, 45.5g Bing Xisuandingzhi, 45.5g TEB 3K, 3g vinylformic acid and 25g deionized water joins in the single port flask, under high-speed stirring in advance emulsification 0.5h to get pre-emulsion for use; It is for use that while adding 0.4g ammonium persulphate, 0.1g sodium hydrogencarbonate and 15g deionized water in another flask obtains initiator solution.
In disposing the four-hole round-bottomed flask of TM, whisking appliance, reflux condensing tube and constant pressure funnel, 20g deionized water and 20g are contained the vinyl polysiloxane emulsion add and wherein stir, be warming up to 80 ℃ behind the logical nitrogen 0.5h; Drop into 10% pre-emulsion and 15% initiator solution simultaneously; Reaction 0.5h begins to drip remaining pre-emulsion and initiator solution simultaneously, dropwises in the 3h, is warming up to 85 ℃ behind the insulation 0.5h and continues reaction 1h; Stop heating; Naturally cool to room temperature, filter discharging, promptly obtain described silicon third copolymer emulsion.
Embodiment 3:
1) contains the preparation of vinyl polysiloxane emulsion: earlier 4g Witco 1298 Soft Acid, 2g X 2073,2g NP-40,60g deionized water are joined in the reaction kettle; Stir fully dissolving; Be warming up to 80 ℃ afterwards; Then 35g octamethylcyclotetrasiloxane, 5g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane mixing an organosilane monomer slowly are added dropwise in 3h in the reaction kettle, insulation reaction 3h naturally cools to room temperature; Be neutralized to neutrality with 10% aqueous sodium carbonate at last, must contain the vinyl polysiloxane emulsion.
The gained emulsion solid content is greater than 35%, molecular weight 2000-5000, and package stability was greater than 3 months.
2) preparation of silicon third copolymer emulsion:
40g is contained vinyl polysiloxane emulsion, 39.5g Bing Xisuandingzhi, 39.5g TEB 3K, 3g vinylformic acid and 20g deionized water joins in the single port flask, under high-speed stirring in advance emulsification 0.5h to get pre-emulsion for use; It is for use that while adding 0.4g ammonium persulphate, 0.1g sodium hydrogencarbonate and 15g deionized water in another flask obtains initiator solution.
In disposing the four-hole round-bottomed flask of TM, whisking appliance, reflux condensing tube and constant pressure funnel, 10g deionized water and 20g are contained the vinyl polysiloxane emulsion add and wherein stir, be warming up to 80 ℃ behind the logical nitrogen 0.5h; Drop into 10% pre-emulsion and 15% initiator solution simultaneously; Reaction 0.5h begins to drip remaining pre-emulsion and initiator solution simultaneously, dropwises in the 3h, is warming up to 85 ℃ behind the insulation 0.5h and continues reaction 1h; Stop heating; Naturally cool to room temperature, filter discharging, promptly obtain described silicon third copolymer emulsion.
The main performance index of gained organosilicon crylic acid latex is following:
Table 1 organosilicon crylic acid latex integrated performance index
Visible by table 1, the high solids content high silicon content organosilicon crylic acid latex for preparing with method of the present invention has the described advantage of this specification sheets really.But embodiment of the present invention does not receive the restriction of above-mentioned case study on implementation; Other any change, the modification of being done under spirit of the present invention and the principle, substitute modes that substitute, make up, simplify, all should be equivalence of not deviating from are included in protection scope of the present invention.
Claims (6)
1. the preparation method of a high solids content (greater than 50%), high organosilicon content (greater than 15%) and low emulsifying agent consumption (less than 2.5%) organosilicon crylic acid latex; Be particularly useful for the organosilicon crylic acid latex of high-grade exterior coating preparation, it is characterized in that the preparation process comprises following steps successively:
(1) contain the preparation of vinyl polysiloxane emulsion:
Witco 1298 Soft Acid, X 2073, emulsifying agent NP-40 and deionized water joined in the reaction kettle stir; Warming-in-water to 60～85 ℃ add an organosilane monomer mixture in 2h-3h, insulation continues reaction 3h; Stop heating; Naturally cool to room temperature, be neutralized to neutrality, obtain containing the vinyl polysiloxane emulsion with 10% aqueous sodium carbonate.
(2) preparation of silicon third copolymer emulsion:
To contain vinyl polysiloxane emulsion, acrylic ester monomer mixture total amount 15%, 20% being added in the reaction kettle of initiator and pH value regulator total amount; Be warming up to 75-85 ℃; The about 30min of isothermal reaction blue light this moment is sufficient and do not have the backflow monomer and produce; Constant temperature drips the mixture of remaining organosilicon and acrylic ester monomer and the mixture of remaining initiator and pH value regulator then, and the dropping time is about 2.5-3.5h; Dropwise isothermal reaction 0.5h, be warming up to 85-95 ℃ then, continue reaction 1-1.5h, stop heating, obtain described organosilicon crylic acid latex.
2. preparation method as claimed in claim 1, it is characterized in that an organosilane monomer mixture by octamethylcyclotetrasiloxane and tetramethyl-tetrem alkene cyclotetrasiloxane with 9: 1-5: 1 mass ratio is formed.
3. preparation method as claimed in claim 1; It is characterized in that said acrylic ester monomer is meant two or more the mixture that is selected from vinylformic acid, methylacrylic acid, TEB 3K, methyl acrylate, ethyl propenoate, propyl acrylate, Bing Xisuandingzhi or the Isooctyl acrylate monomer, concrete consumption and proportioning are according to the purposes decision of product.
4. preparation method as claimed in claim 1; It is characterized in that compound emulsifying agent is at least two kinds of negatively charged ion-nonionic emulsifying agents that material is formed in X 2073, sodium lauryl sulphate or the octyl group polyethenoxy ether class, and the proportioning of negatively charged ion and nonionic is 4: 1～2: 1.
5. preparation method as claimed in claim 1; It is characterized in that catalyzer is a Witco 1298 Soft Acid; Acrylic or methacrylic acid, they also have the emulsifying effect of tensio-active agent concurrently simultaneously both as the acid catalyst of ring-opening polymerization; Especially the latter be because as can participating in main chain polymeric surface active monomer, can guarantee under the stable prerequisite of polymer emulsion product, significantly to reduce the total consumption of emulsifying agent.
6. preparation method as claimed in claim 1 is characterized in that initiator is a persulphate, mainly is ammonium persulphate or Potassium Persulphate; Molecular weight regulator is a lauryl mercaptan; Said PH buffer reagent is sodium hydrogencarbonate, Sodium phosphate, dibasic or SODIUM PHOSPHATE, MONOBASIC.
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Application publication date: 20121128 |